Liquid 2-hydroxy-4-alkoxybenzophenone ultraviolet light stabilizers for polymers

ABSTRACT

LIQUID 2-HYDROXY-4-ALKOXYBENZOPHENONES ARE PREPARED WHERE THE ALKOXY GROUP IS A MIXTURE OF RANDOM BRANCHED ALKYL GROUPS OF 6-10 CARBON ATOMS. THEY ARE USEFUL AS ULTRAVIOLET LIGHT STABILIZERS FOR POLYMERS, E.G. VINYL CHLORIDE POLYMERS AND MONOOLEFIN POLYMERS.

United States ?atent C) 3,729,442 LIQUID Z-HYDROXY 4-ALKOXYBENZOPHE-NONE ULTRAVIOLET LIGHT STABILIZERS FOR POLYMERS Ingenuin A.Hechenbleikner, Cincinnati, Ohio, assignor to Carlisle Chemical Works,Inc., Reading, Ohio No Drawing. Original application Feb. 11, 1970, Ser.No. 10,608, now Patent No. 3,658,910. Divided and this application Jan.7, 1972, Ser. No. 216,277

Int. Cl. C08f 45/58 US. Cl. 260-4535 F 7 Claims ABSTRACT OF THEDISCLOSURE Liquid 2-hydroxy-4-alkoxybenzophenones are prepared where thealkoxy group is a mixture of random branched alkyl groups of 6-10 carbonatoms. They are useful as ultraviolet light stabilizers for polymers,e.g. vinyl chloride polymers and monoolefin polymers.

This is a division of application Ser. No. 10,608, filed Feb. 11, 1970,now Pat. 3,658,910.

The present invention relates to 2-hydroXy-4-alkoxybenzophenones.

It is known to prepare solid 2-hydroxy-4-octoxy-benzophenones whereinthe octyl group is either n-octyl or 2- ethylhexyl. Such materials havebeen utilized as ultraviolet light stabilizers. Compounds of this typeare shown in US. Pat. 2,861,105 and German Offenlegungschrift 1,806,870.However, due to the fact that such products are solids they have certaininherent disadvantages.

It is an object of the present invention to prepare novel liquid2-hydroxy-4-alkoxybenzophenones.

Another object is to use such alkoxy compounds as ultravioletstabilizers for polymers.

An additional object is to prepare such stabilizers having greatercompatibility with most resins than conventional solid ri-alkoxycontaining ultraviolet stabilizers.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific example, while indicating preferred embodimentsof the invention, are given by Way of illustration only, since variouschanges and modifications within the spirit and scope of the inventionwill become apparent to those skilled in the art from this detaileddescription.

It has now been found that these objects can be attained by preparing2-hydroxy-4-alkoxybenzophenones of the formula OH II 0 where R is amixture of random branched alkyl groups having 6 to 10 carbon atoms andare of the oxo type and are hereinafter identified as isoalkyl groups.

The isoalkoxy compounds of the invention are prepared by reacting2,4-dihydroxybenzophenone with an 0x0 alkyl halide (also called isoalkylhalide) of the formula RX where R is as defined above and X is chlorine,bromine or iodine. Examples of such compounds are oxo octyl chloride,0X0 octyl bromide, 0x0 octyl iodide, oxo hexyl chloride, 0x0 decylchloride, oxo heptyl chloride, oxo nonyl chloride.

The 0x0 halides are prepared in conventional fashion from thecorresponding 0X0 alcohols, e.g. oxo octyl alcohol, oxo hexyl alcohol,oxo decyl alcohol. Such "ice compounds are also known as isooctanol,isohexanol and isodecanol and are a mixture of isomeric alcohols made bythe 0x0 process. As applied to the 0x0 process alcohols the term isosignifies a mixture of branched chain primary alcohols, see Kirk-OthmerEncyclopedia of Chemical Technology, 2nd edition, vol. 14, pages 373374.A typical commercially available isooctanol has the analysis3,4-dimethyl-l-hexanol 20%, 3,5-dimethyl l-hexanol 30%,4,5-dimethyl-1-hexanol 30%, 3-methyll-heptanol and S-methyl-l-heptanoltogether 15% and unidentified alcohol 5%. A typical commerciallyavailable isodecanol is a mixture of a plurality of primary saturatedalcohols having ten carbon atoms. There is a major proportion of amixture of trimethyl heptanols and small amounts of other isomericprimary saturated decanols. Another commercially available isoalkanol isAlphanol 79 a mixture of primary saturated alkanols of 7, 8 and 9 carbonatoms having methyl side chains.

The terms isoalkyl and isoalkoxy as used in the present specificationand claims are used in the manner set forth in the Kirk-Othmer citationto denote the complex mixture of isomers produced as a result of using0x0 process starting alcohols and halides. In general such mixturescontain at least 10% of at least three different branched chain isomers.

The compounds of the invention are thus 2-hydroxy-4-isohexoxybenzophenone, 2 hydroxy-4-isoheptoxybenzophenone,2-hydroxy-4-isooctoxybenzophenone, Z-hydroxy- 4-isononoxybenzophenone,and 2 hydroxy-4-isodecoxybenzophenone. Obviously mixtures of suchcompounds can also be used. All of the isoalkoxy compounds of thepresent invention are liquids at room temperature and considerablybelow, the 4-isooctoxy-2-hydroxy benzophenone can be liquid attemperatures down to 20 C., e.g. 0 C.

Unless otherwise indicated, all parts and percentages are by weight.

The compounds of the present invention are useful as ultraviolet lightstabilizers for polymers, e.g. halogen containing resins (preefrablyvinyl chloride polymers) and olefin polymers (preferably polypropylene),particularly solid polymers.

As the halogen containing resins there can be used resins made fromvinylidene compounds such as vinyl chloride, vinylidene chloride, vinylchloroacetate, chlorostyrenes, vinyl bromide and chlorobutadienes.

Such vinylidene compounds may be polymerized alone or in admixture witheach other or with vinylidene compounds free from halogen. Among thehalogen free ma terials which can be copolymerized with the halogencontaining vinylidene compounds, e.g. vinyl chloride, are vinyl estersof carboxylic acids, e.g. vinyl acetates, vinyl propionate, vinylbutyrate and vinyl benzoate, esters of unsaturated acids, e.g., alkyland alkenyl acrylates such as methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate and allyl acrylate as Well as the correspondingmethacrylates, e.g. methyl methacrylate and butyl methacrylate, vinylaromatic compounds, e.g. styrene, p-ethyl styrene, divinyl benzene,vinyl naphthalene, a-methyl styrene, p-methyl styrene, dienes such asbutadiene and isoprene, unsaturated amides such as acrylamide,methacrylamide and aerylanilide and the esters of 0:,[3-1111821111-rated carboxylic acids, e.g. the methyl, ethyl, propyl, butyl, amyl,hexyl, heptyl, octyl, allyl, methallyl and phenyl esters of maleic,crotonic, itaconic and fumaric acids and the like. Specific examples ofsuch esters are diethyl maleate, dibutyl maleate and dibutyl fumarate.

The copolymers in which at least 50% of the copolymer is made from ahalogen containing vinylidene compound such as vinyl chloride arepreferably treated according to the invention.

The stabilizers of the present invention are also effective whenintimately mixed With halogen containing resins in which part or all ofthe halogen is introduced into a preformed resin, e.g. chlorinatedpolyvinyl acetate, chlo rinated polystyrene, chlorinated polyethylene,chlorinated polyvinyl chloride, chlorinated natural and syntheticrubbers and rubber hydrochloride.

Typical examples of copolymers include vinyl chloridevinyl acetate (95:5weight ratio), vinyl chloride-vinyl acetate (87: 13 weight ratio), vinylchloride-vinyl acetatemaleic anhydride (86: 13:1 weight ratio), vinylchloridevinylidene chloride (95 weight ratio), vinyl chloride diethylfumarate (95 :5 weight ratio), vinyl chloride-trichloroethylene (95:5Weight ratio).

The resin, e.g. polyvinyl chloride, can either be plasticized orunplasticized. As the plasticizer there can be employed conventionalmaterials such as dioctyl phthalate, octyl decyl phthalate, tricresylphosphate, Z-ethylhexyl diphenyl phosphate, dodecyl dicresyl phosphate,tributyl acetyl citrate, dioctyl sebacate, dibutyl sebacate, etc. Theplasticizer is used in conventional amount, e.g. to 100 parts for each100 parts of the vinyl chloride containing resin.

The stabilizers of the present invention are used in an amount of 0.05to parts, preferably 0.1 to 10 parts per 100 parts of halogen containingresin.

There can also be incorporated 0.1 to 10 parts per 100 parts of thehalogen containing resin of a metal salt stabilizer. Thus, there can beused barium, strontium, calcium, cadmium, zinc, lead, tin, magnesium,cobalt, nickel, titanium and aluminum salts of phenols, aromaticcarboxylic acids, fatty acids and epoxy fatty acids.

Examples of suitable salts include barium di(nonylphenolate), strontiumdi(nonylphenolate), strontium di- (amylphenolate), bariumdi(octylphenolate), strontium di(octylphenolate), bariumdi(nony1-o-cresolate), lead di(octylphenolate) cadmium-Z-ethylhexoate,cadmium laurate, cadmium stearate, zinc caprylate, cadmium capraote,barium stearate, barium Z-ethyl-hexoate, barium laurate, bariumriclnoleate, lead stearate, aluminum stearate, magnesium stearate,calcium octoate, calcium stearate, cadmium naphthanate, cadmiumbenzoate, cadmium p-tert, butylbenzoate, barium octyl salicylate,cadmium epoxy stearate, strontium epoxy stearate, cadmium salt ofepoxidized acids of soybean oil, and lead epoxy stearate.

In plastisol formulations, there is preferably also included from 0.1 to10 parts per 100 parts of resins of an epoxy vegetable oil such asepoxidized soybean oil or epoxidized tall oil.

Also there can be incorporated a phosphite, e.g. a alkyl, aryl oraralkyl phosphite in an amount of 0.1 to 10 parts per 100 parts ofresin. Typical of such phosphites are triphenyl phosphite, tris decylphosphite, decyl diphenyl phosphite, di(p-tert butylphenyl) phenylphosphite, diphenyl o-cresyl phosphite, trioctyl phoshite, tricresylphosphite and tribenzyl phosphite.

The compounds of the present invention are also sta bilizers formonolefin polymers such as polyethylene, polypropylene, ethylenepropylene copolymers (e.g. 50:50, 80:20 and 20:80), ethylene-monolefincopolymers wherein the monoolefin has 4-10 carbon atoms and is presentin a minor amount, e.g. ethylene-butene-l copolymer (95 :5) andethylenedecene-l copolymer (90:10). Furthermore, they can be used tostabilize natural rubber, styrene-butadiene rubber (SBR rubber), e.g.(75% butadiene, styrene) and EPDM rubbers and acrylonitrile-butadienestyrene terpolymers (ABS).

As the EPDM rubber there can be employed many of the commerciallyavailable EPDM rubbers. The EPDM rubber normally contains to 70 molarpercent (preferably 50 to 60 molar percent) of ethylene, 65 to 20 molarpercent (preferably to 45 molar percent propylene) and 1 to 15 molarpercent (preferably 3 to 5 molar percent) of the nonconjugatedpolyolefin. Usually the polyolefin is not over 10 molar percent. Theethylene and propylene can each be 5 to molar percent of thecomposition.

As used in the present specification and claims the term nonconjugatedpolyolefin includes aliphatic unconjugated polyene hydrocarbons andcycloaliphatic nonconjugated polyene hydrocarbons, e.g., endocyclicdienes. Specific examples of suitable nonconjugated polyolefins includepentadiene-1,4; hexadiene-1,4; dicyclopentadiene, methyl cyclopentadienedimer, cyclodedecatriene, cyclooctadiene- 1,5; S-methylene-Z-norbornene.

Specific examples of suitable terpolymers are the Royalenes whichcontain 55 mole percent ethylene, 40 to 42 mole percent propylene and 3to 5 mole percent dicyclopentadiene; Enjay terpolymers, e.g., ERP-404 ofEnjay and Enjay 3509 which contains about 55 mole percent ethylene, 41mole percent propylene and 4 mole percent S-methylene-Z-norbornene;Nordel; a terpolymer of 55 mole percent ethylene, 40 mole percentpropylene and 5 mole percent hexadiene-1,4. Another suitable terpolymeris the one containing 50 mole percent ethylene, 47 mole percentpropylene and 3 mole percent 1,5-cyclooctadiene (dutrel).

Examples of EPDM rubbers are given in US. Pats. 2,933,480; 3,000,866;3,063,973; 3,093,620; 3,093,621; and 3,136,739, in British Patent880,904 and in Belgian Patent 623,698.

Terpolymers and other EPDM rubbers from ethylene, propylene anddicyclopentadiene are exemplified in Tarney Patent 3,000,866; AdamekPat. 3,136,739 and Dunlop (British Pat. 880,904. EPDM rubbers fromethylene, propylene and 1,4-hexadiene are exemplified in Gresham Pat.2,933,480. As in Gresham other suitable nonconjugated diolefins are1,4-pentadiene; 2-methyl-l,5-hexadiene, 3,3-dimethyl-1,5-hexadiene,1,7-octadiene, 1,9-decadiene, 1,19-eicosadiene, 1,9-octadecadiene,6-methyl-1,5-heptadiene, methyl-1,6-octadiene,11-ethyl-l,ll-tridecadiene.

EPDM rubbers from ethylene, propylene and S-methyl- 2-norbornene areexemplified in US. Patent 3,093,621. Suitable norbornadienes e.g.,Z-methyl norbornadiene, 2- ethyl norbornadiene, 2-n-heptyl norbornadieneare shown in Gladding Patent 3,063,973 and bicyclo compounds such asbicyclo (2,2,2) heptadiene-2,5 are shown in Dunlop (British) Patent880,904. The use of cyclooctadiene-1,5 and other cyclodienes is shown inMontacatini (Belgium) Patent 623,698. Thus there can be used in makingthe EPDM elastomer 1,4-cycloheptadiene, 1,4-cyclooctadiene, 1,6cyclodecadiene, 1,5-cyclododecadiene, 1,7-cyclodecadiene, 1,5,9cyclododecatriene, 1-methyl-1,5-cyclooctadiene.

The compounds of the present invention are normally employed in anamount of at least 0.01 and usually 0.1% to 10% by weight of the polymerthey are intended to stabilize.

There can also be included conventional sulfur containbenzyl3,3-thiodipropionate, lauryl myristyl-3,3-thiodipropionate,diphenyl-3,3-thiodipropionate, di-p-methoxyphenyl 3,3'-thiodipropionate,didecyl-3,3'-thiodipropionate, dibenzyl 3,3 thiodipropionate,diethyl-3,3-thiodipropionate, lauryl ester of 3-methy1mercapto propionicacid, lauryl ester of 3-butyl-mercapto propionic acid, lauryl ester of3-1aurylmercaptopropionic acid, phenyl ester of 3-octylmercaptopropionic acid, lauryl ester of 3-phenylmercapto propionic acid, laurylester of 3-benzylmercapto propionic acid, lauryl ester of 3-(p-methoxy)phenylmercapto propionic acid, lauryl ester of 3-cyclohexylmercaptopropionic acid, lauryl ester of 3-hydroxymethy1mercapto propionic acid,myristyl ester of 3-hydroxyethylmercapto propionic acid, octyl ester of3-methoxymethylmercapto propionic acid, dilauryl ester of3-hydroxymethylmercapto propionic acid, myristyl ester of3-hydroxyethylmercapto propionic acid, octyl ester of3-methoxymethylmercapto propionic acid, dilauryl ester of3-carboxylmethylmercapto propionic acid, dilauryl ester of3-carboxypropylmercapto propionic acid, dilauryl-4,7-dithiasebacate,dilauryl- 4,7,8,l1 tetrathiotetradecandioate,dimyristyl-4,11-dithiatetradecandioate lauryl3-benzothiazylmercaptopropionate. Preferably the esterify alcohol is analkanol having 10 to 18 carbon atoms. Other esters of betathiocarboxylic acids set forth in Gribbins Patent 2,519,744 can also beused.

Other beta thiocarboxylic acids include stearyl(1,2-dicarboethoxyethylthio) acetate, stearyl(1,2-dicarbolauryloxyethylthio) acetate or the like. Compounds of thistype can be made by addition of an alkyl etser of mercaptoacetic acid toa dialkyl ester of maleic acid. Similar beta thiocarboxyl compounds canbe used which are made by addition of an RSH compound across the maleicester double bond and where R is alkyl, aryl, alkylcarboxyalkyl,arylcarboxyalkyl or aralkyl. Examples of such compounds aredecylthiodilauryl maleate, phenylthiodioctyl maleate, cetyl(1,2-dicarboethoxyethylthio) propionate and benzylthiodimyristylmaleate.

Similarly useful beta thiocarboxyl synergistic compounds can be preparedby addition of the RSH (mercaptan) compounds as defined above across thedouble bond of dialkyl itaconates, citraconates, fumarates or trialkylaconitates, e.g. the addition product of lauryl mercaptan with dibutylitaconate, the addition product of the stearyl ester of mercaptoaceticacid with dilauryl itaconate, the addition product of butyl mercaptanwith dilauryl citraconate, the addition product of lauryl mercaptan withtributyl aconitate, the addition product of the lauryl ester ofmercaptopropionic acid with triethyl aconitate.

The thermal stability of the polypropylene and other monoolefin polymeris adversely affected by impurities including residual catalyst. Whenthermal stability is important in addition to ultraviolet light andoxidative stability it has been found valuable to include polyvalentmetal salts of fatty acids in an amount of 0.01-10% preferably 0.1-5%,in the monoolefin polymer formulations. Examples of such salts arecalcium stearate, calcium 2- ethylhexoate, calcium octate, calciumoleate, calcium ricinoleate, calcium myristate, calcium palmitate,calcium laurate, barium laurate, barium stearate, magnesium stearate aswell as zinc stearate, cadmium laurate, cadmium octoate, cadmiumstearate and the other polyvalent metal salts of fatty acids set forthpreviously.

There can also be added phenolic antioxidants in an amount of 0.01l%,preferably 0.1-%. Examples of such phenols include2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, propyl gallate,4,4-thiobis(6-t-butyl-mcresol), 4,4 cyclohexylidene diphenol,2,5-di-t-amy1 hydroquinone, 4,4 butylidene bis (y-t-butyl-m-cresol),hydroquinone monobenzyl ether, 2,2 methylene-bis(4- methyl 6t-butylphenol) 2,6-butyl 4 decyloxyphenol, 2-t-butyl 4 dodecyloxyphenol,2-t-butyl-4-dodecyloxyphenol, Z-t-butyl 4 octadecyloxyphenol, 4,4methylene-bis(2,6 di-t-butylphenol), p-aminophenol,N-lauryloxy-p-aminophenol, 4,4 thiobis(3 methyl-G-t-butylphenol), bis[o(1,3,3 tetramethylbutyl)phenol] sulfide, 4-acetyl B resorcylic acid, Astage p-t-butylphenolformaldehyde resin, 4 dodecyloxy 2hydroxybenzophenone, 3-hydroxy 4 (phenylcarbonyl) phenyl palmitate,ndodecyl ester of 3-hydroxy 4 (phenylcarbonyl) phenoxyacetic acid, andt-butylphenol as well as those shown in Belgian Pat. 710,873 and FrenchPat. 1,536,020.

The use of epoxy compounds in an amount of 0.01- 5% in the polymercompositions is also valuable. Examples of such epoxy compounds includeepoxidized soya bean oil, epoxidized lard oil, epoxidized olive oil,epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil,epoxidized corn oil, epoxidized tung oil, epoxidized cotton-seed oil,epichlorohydrin bisphenol A resins (epichlorohydrindiphenylolpropaneresins), phenoxy-propylene oxide, butoxypropylene oxide, epoxidizedneopentylene oleate, glycidyl epoxystearate, epoxidized a-olefins,epoxidized glycidyl soyate, dicyclopentadiene dioxide, epoxidized butyltallate, styrene oxide, dipentene dioxide, glycidol, vinyl cyclohexenedioxide, glycidyl ether of resorcinol, glycidol ether of hydroquinone,glycidyl ether of 1,5 dihydroxynaphthalene, epoxidized linseed oil fattyacids, allyl glycidyl ether, butyl glycidyl ether, cyclohexane oxide, 4(2,3 epoxypropoxy) acetophenone, mesityl oxide epoxide, 2-ethyl 3 propylglycidamide, glycidyl ethers of glycerine, pentaerythritol and sorbitol,and 3,4 epoxycyclohexane 1,1 dimethanol bis-9, 1 0-epoxyste arate.

The compounds of the present invention can also be employed inconjunction with phosphites and thiophosphites as antioxidants andstabilizers for olefin polymers. The phosphite or thiophosphite isemployed in an amount of 0.01 to 10% of the polymer (or other material)being stabilized. Thus there can be employed tristearyl phosphite,trilauryl trithiophosphite, trilauryl 'phosphite or any of thephosphites or thiophosphites in Friedman Pat. 3,039,993, Friedman Pat.3,047,608, Friedman Pat. 3,053,- 878 or Larrison Pat. 3,341,629.

The liquid 2-hydroxy 4 isoalkoxybenzophenones of the present inventionhave numerous advantages over the solid 2-hydroxy-4-alkoxybenzophenoneultraviolet light stabilizers.

(1) They can be handled as liquids.

(2) They have greater solubility in most solvents and plasticizers.

(3) They can be manufactured in higher yields.

(4) They have greater compatibility with most resins and hence are lesssubject to blooming and exudation.

(5) They are less subject to Water extraction from plastics due to thisgreater compatibility.

(6) They give superior performance in some resins due to greatercompatibility.

EXAMPLE 1 0x0 4-octoxy-Z-hydroxybenzophenone-(4-isooctoxy-Z-hydroxybenzophenone) Reagents:

2,4-dihydroxybenzophenone mole 1 Sodium iodide mole 0.1 Oxo octylchloride (isooctyl chloride) moles 1.2 Acetone ml 1000 Sodium carbonate"moles 1.2

The reagents were added to a suitable pressure vessel and heated at C.for a total of 4 hours with mechanical agitation. At the end of thisperiod the mixture was transferred to a suitable vessel and the majorpart of the acetone was stripped for reuse. The residue was drowned in 4liters of water and the upper layer was separated, transferred to adistillation flask and distilled. The distillate coming over between220-225" C. at 1 mm. was collected. A small forerun was discarded. Theyield of product was 0.97 mole (97%). (In contrast German Pat. 1,806,870shows a maximum yield of 59% of 4-n-octoxy-2-hydroxybenzophenone.)

The physical properties of the isooctoxy product of Example 1 comparedto the n-octoxy isomer are set forth in Table 1.

TABLE 1 TABLE 3 Typical properties Isooctoxy n-Octoxy A B FormWeathor-Ometer test, hours 200 180 Molecular Weight 326 326 Appearancesolidification point, 0..-- 48 5 Pour point, 0.0. .6--- 1 "i 66 1 Slightyellow. i iggzg g figggg j 1%; i Nont 'lgei same formulations were usedasin TableZbut after boiling Color, percent transmis nwa er or gfg jgggfi 3 3 These 0x0 benzophenones can also be used with any Volatiles,percent 0. 0 10 of the conventional nickel chelates such as nickelacetyl i fifiiiiiiiliua'ziaa'aaatiiii1313:1211: 5% 0.63 donate ll'thiobiflteoflylphenolato) n-butylamine nickel (II), and other nickelcompounds. These nickel i fi ivii i ir y tiiiae powder compounds arebelieved to be carbonyl oxygen triplet :Clear glass at -20 C. quenchersand are useful as ultraviolet stabilizers par- Mmtenticularly in thepresence of the 0x0 benzophenones of 4 isohexoxy 2 hydroxybenzophenonewas prepared in similar manner by replacing the isooctyl chloride inExample 1 by 1.2 moles of isohexyl chloride and 4-isodecoxy 2,4hydroxybenzophenone was prepared by replacing the isooctyl chloride inExample 1 by 1.2 moles of isodecyl chloride.

EXAMPLE 2 The ultraviolet stabilizing properties of 4isooctoxy-2-hydroxybenzophenone was tested in an impact modified polyvinyl chloridein both a clear and pigmented formulation.

The test recipes were as follows:

Geon 103 EP (polyvinyl chloride), parts 100 10 K-120N (acrylic modifier)3 Kane Ace B-l2 (acrylic modifier)--- l5 1 Advawax 135 (distearylazelate) 0. 75 0. 7 $llg-l80 (dibutylt-in isooctyl thioglyeolate) 2 1%4-isooctoxy-2-hydroxybenzophenone 0. 5 0. 6

EXAMPLE 3 The procedure of Example 2 was repeated but the K-lZON and theKane ACB-l2 were omitted to give a polyvinyl chloride composition whichwas not impact modified. The 4-isooctoxy-2-hydroxybenzophenone was alsoan effective ultraviolet light stabilizer in such formulations bothclear and pigmented.

EXAMPLE 4 4-isooctoxy 2 hydroxybenzophenone was compared with4-n-octoxy-2-hydroxybenzophenone as ultraviolet stabilizers inpolypropylene. The compositions and results are set forth in Tables 2and 3.

TABLE 2 Polypropylene, parts 100 10 DSlDP (distearyl thiodipropionate)0.3 0. 3 Irganox 1010 (tetrakis ester of 4-hydroxy2,6-di-tbutylphenylpropionic acid with pentaery'thritol) 0. l 0. 14-isooctoxy-Z-hydroxybenzo enrme 0. 5 l-n-oetoxy2-hydroxybenzophenone 0.5 Weather-Ometer test, hours.. 325 300 Appearance at end of test 1 Thehours are hours to failure as judged by the flex test. 1 Colorless. 3Irregular yellow.

the present invention. A typical formulation is as follows:

Distearylthiodipropionate 0.3 Pentaerythritol tetrakis (4-hydroxy-2,6-di-t-butylphenylpropionate) 0.1

These ingredients were mixed with the polypropylene and milled into a 20mil film in the conventional manner.

This combination lasted 600 hours in the Weather- Ometer beforedeterioration.

What is claimed is:

1. A stabilized polymer composition wherein the polymer is a memberselected from the group consisting of vinyl halide polymers, vinylidenehalide polymers, halogenated polyvinyl acetate, halogenated polystyrene,halogenated polyethylene, halogenated polyvinyl chloride, halogenatedrubber, halobutadiene polymer and rubber hydrohalide and olefinpolymers, said polymer subject to deterioration due to ultra-violetlight and having admixed therewith a stabilizingly effective amount of aZ-hydroxy- 4-isoalkoxybenzophenone which is liquid at room temperaturehaving 6 to 10 carbon atoms in the isoalkoxy group containing a mixtureof branched chain groups produced by the 0x0 process.

2.. A composition according to claim 1 wherein any halogen present inthe polymer is chlorine.

3. A composition according to claim 2 wherein the2-hydroxy-4-isoalkoxy-benzophenone is a liquid at temperatures at leastas low as 0 C.

4. A composition according to claim 1 wherein the polymer is a vinylchloride polymer.

5. A composition according to claim 1 wherein the polymer is an olefinpolymer.

6. A composition according to claim 5 wherein the polymer is a propylenepolymer.

7. A composition according to claim 1 wherein the benzophenone compoundis 4-isooctoxy-2-hydroxybenzophenone which is liquid at temperaturesdown to 20 C.

References Cited UNITED STATES PATENTS 2,861,053 11/1958 Lappin et al.26045.95 2,976,259 3/1961 Hardy et a1 260-4595 MAURICE J. WELSH, JR.,Primary Examiner V. P. HOKE, Assistant Examiner US. Cl. X.R. 260-8 10,814

